Different sampling media (moss, lichen and attic dust) were used for monitoring the distribution of 15 elements, including certain trace elements, in the vicinity of an intensively exploited copper mine in the east of the Republic of Macedonia. Moss species (Hypnum cupressiforme and Campothecium lutescens), epiphytic lichens (Hypogymnia physodes and Evernia prunastri) and attic dust were collected for comparative analysis for monitoring air pollution. In both cases (lithological and anthropogenic affected areas) for the distribution of elements, the sampling media follows the expression capabilities: attic dust > moss > lichens. Enrichment factors M/L—moss vs. lichen, for plant response to elements distribution and D/L—attic dust vs. lichen, for historical response of elements distribution were significant for Cu and Ni, which were singled out as the main markers for anthropogenic and geogenic distribution. The factor analysis highlighted geogenic (F1: Ni-Cr-Cd-Fe-Al-K-Mn-Zn) and anthropogenic (F2: As-Cu-Pb) association of elements from three types of media samples. For anthropogenic affected areas, T value and F value for Cu content were significant at p < 0.05 and higher enrichment factors were obtained for lichen, moss and attic dust media (3.8, 5.0 and 5.7, respectively). Spatial distribution for element deposition (with emphasis on Cu and Ni) is not disturbed by the significant differences in the sampling media matrix. Treated sample materials (attic dust, moss, lichen) are shown to be useful in determining an anthropogenic impact, as well as the chemical properties or geological background on orographic diverse terrain in the presence of complex geological structure.